1-Isopropyl­ideneamino-1H-tetra­zol-5-amine

He, C.-L.; Du, Z.-M.; Tang, Z.-Q.; Cong, X.-M.; Meng, L.-Q.

doi:10.1107/S1600536809024994

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1760

doi:10.1107/S1600536809024994

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1-Isopropylideneamino-1H-tetrazol-5-amine

Chun-Lin He,^a Zhi-Ming Du,^a ^* Zheng-Qiang Tang,^a Xiao-Min Cong ^a and Ling-Qiao Meng ^a

^aState Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, People's Republic of China
^*Correspondence e-mail: duzhiming430@sohu.com

(Received 25 June 2009; accepted 29 June 2009; online 4 July 2009)

The molecule of the title compound, C₄H₈N₆, assumes an approximately planar structure, the methyl C atoms and the C atom to which they are bonded being out of the mean tetrazole ring plane by 0.108 and 0.139, and 0.144 Å, respectively. π–π stacking between parallel tetrazole rings [centroid–centroid distance = 3.4663 (11) Å] is observed in the crystal structure. Intermolecular N—H⋯N hydrogen bonding further helps to stabilize the crystal structure.

Related literature

For the preparation of the title compound, see: Gaponnik & Karavai (1984 ). For general background, see: Galvez-Ruiz et al. (2005 ); Joo et al. (2008 ). For a related structures, see: Lyakhov et al. (2005 ).

Experimental

Crystal data

C₄H₈N₆
M_r = 140.16
Monoclinic, P 2₁ /c
a = 7.488 (2) Å
b = 7.4238 (19) Å
c = 11.997 (3) Å
β = 97.145 (3)°
V = 661.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 93 K
0.43 × 0.43 × 0.33 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: none
5172 measured reflections
1520 independent reflections
1334 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.088
S = 1.00
1520 reflections
101 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6A⋯N2ⁱ	0.890 (16)	2.200 (17)	3.0600 (16)	162.6 (13)
N6—H6B⋯N1ⁱⁱ	0.876 (15)	2.118 (15)	2.9770 (16)	166.4 (14)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+2, -y, -z+1.

Data collection: CrystalClear (Rigaku, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809024994/xu2546sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024994/xu2546Isup2.hkl

checkCIF report

Comment top

1,5-diaminotetrazole and its derivatives have received an increasing interest as a class of nitrogen-rich energetic materials during the last years.These compounds exhibit prospective application in generation of gases, propellants and other combustible and thermally decomposing systems (Galvez-Ruiz et al., 2005; Joo, et al. 2008). The title compound had been prepared by Gaponnik & Karavai, but its crystal structure hadn't been reported, therefore, the structure of the title compound has been determined in our present work.

The crystal structure of the title compound is presented in Fig. 1, The bond distances and bond angles in the title compound are similar to the corresponding distances and angles reported by Lyakhov et al. (2005). The molecule is almost planar with only C2, C3 and C4 being out of the mean plane of the tetrazole ring by 0.108, 0.144 and 0.139 Å, respectively.

In the crystal structure the molecules are linked to each other via N—H···N hydrogen bonding (Table 1), forming a three dimensional network structure). The offset face-to-face π-π contact between the tetrazole rings, related by an inversion center, further helps to stabilize the crystal structure; centroid-centroid distance being 3.4663 (11) Å.

Related literature top

For the preparation, see: Gaponnik & Karavai (1984). For general background, see: Galvez-Ruiz et al. (2005); Joo et al. (2008). For a related structures, see: Lyakhov et al. (2005).

Experimental top

The title compound was prepared according to the literature method (Gaponnik & Karavai, 1984). The purity of the compound was checked by determining its melting point, m.p. 445–446 K. Crystals suitable for X-ray structure determination were obtained by slow evaporation of an acetone solution at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

1-Isopropylideneamino-1H<ι>-tetrazol-5-amine top

Crystal data top

C₄H₈N₆	F(000) = 296
M_r = 140.16	D_x = 1.407 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 445 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.488 (2) Å	Cell parameters from 2076 reflections
b = 7.4238 (19) Å	θ = 3.1–27.5°
c = 11.997 (3) Å	µ = 0.10 mm⁻¹
β = 97.145 (3)°	T = 93 K
V = 661.7 (3) Å³	Block, colourless
Z = 4	0.43 × 0.43 × 0.33 mm

Data collection top

Rigaku Saturn724+ diffractometer	1334 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.024
Graphite monochromator	θ_max = 27.5°, θ_min = 3.2°
Detector resolution: 28.5714 pixels mm^-1	h = −9→9
multi–scan	k = −8→9
5172 measured reflections	l = −15→15
1520 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.036	w = 1/[σ²(F_o²) + (0.045P)² + 0.16P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.088	(Δ/σ)_max < 0.001
S = 1.00	Δρ_max = 0.28 e Å⁻³
1520 reflections	Δρ_min = −0.17 e Å⁻³
101 parameters

Crystal data top

C₄H₈N₆	V = 661.7 (3) Å³
M_r = 140.16	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.488 (2) Å	µ = 0.10 mm⁻¹
b = 7.4238 (19) Å	T = 93 K
c = 11.997 (3) Å	0.43 × 0.43 × 0.33 mm
β = 97.145 (3)°

Data collection top

Rigaku Saturn724+ diffractometer	1334 reflections with I > 2σ(I)
5172 measured reflections	R_int = 0.024
1520 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.28 e Å⁻³
1520 reflections	Δρ_min = −0.17 e Å⁻³
101 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.90734 (13)	0.19832 (13)	0.44509 (8)	0.0177 (2)
N2	0.84796 (13)	0.34792 (13)	0.38501 (8)	0.0182 (2)
N3	0.78344 (13)	0.46815 (13)	0.44617 (8)	0.0181 (2)
N4	0.79984 (12)	0.39605 (12)	0.55284 (7)	0.0144 (2)
N5	0.74880 (12)	0.46344 (12)	0.65193 (7)	0.0165 (2)
N6	0.91309 (15)	0.12338 (14)	0.63884 (8)	0.0223 (2)
C1	0.87689 (14)	0.23122 (15)	0.55029 (9)	0.0153 (2)
C2	0.66745 (14)	0.61599 (15)	0.65364 (9)	0.0169 (2)
C3	0.61800 (16)	0.74455 (16)	0.55860 (10)	0.0215 (3)
H3A	0.7275	0.7992	0.5366	0.026*
H3B	0.5397	0.8391	0.5825	0.026*
H3C	0.5545	0.6795	0.4945	0.026*
C4	0.62021 (16)	0.66948 (17)	0.76627 (10)	0.0232 (3)
H4A	0.6608	0.5760	0.8213	0.028*
H4B	0.4895	0.6838	0.7624	0.028*
H4C	0.6794	0.7837	0.7891	0.028*
H6A	0.887 (2)	0.156 (2)	0.7063 (14)	0.033 (4)*
H6B	0.972 (2)	0.025 (2)	0.6261 (13)	0.037 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0210 (5)	0.0176 (5)	0.0146 (5)	0.0012 (4)	0.0026 (4)	−0.0006 (4)
N2	0.0214 (5)	0.0174 (5)	0.0161 (5)	0.0008 (4)	0.0036 (4)	−0.0003 (4)
N3	0.0230 (5)	0.0186 (5)	0.0133 (4)	0.0000 (4)	0.0045 (4)	0.0006 (4)
N4	0.0175 (5)	0.0144 (5)	0.0117 (4)	0.0008 (3)	0.0030 (3)	−0.0010 (3)
N5	0.0192 (5)	0.0183 (5)	0.0127 (4)	−0.0001 (4)	0.0042 (4)	−0.0031 (4)
N6	0.0337 (6)	0.0202 (5)	0.0137 (5)	0.0093 (4)	0.0062 (4)	0.0008 (4)
C1	0.0152 (5)	0.0167 (5)	0.0141 (5)	−0.0007 (4)	0.0026 (4)	−0.0019 (4)
C2	0.0151 (5)	0.0167 (5)	0.0190 (6)	−0.0019 (4)	0.0025 (4)	−0.0029 (4)
C3	0.0243 (6)	0.0185 (6)	0.0220 (6)	0.0043 (4)	0.0045 (5)	0.0002 (5)
C4	0.0261 (6)	0.0244 (6)	0.0196 (6)	0.0046 (5)	0.0043 (5)	−0.0055 (5)

Geometric parameters (Å, º) top

N1—C1	1.3326 (14)	N6—H6B	0.878 (17)
N1—N2	1.3678 (13)	C2—C4	1.4924 (16)
N2—N3	1.2870 (13)	C2—C3	1.4977 (16)
N3—N4	1.3784 (13)	C3—H3A	0.9800
N4—C1	1.3549 (14)	C3—H3B	0.9800
N4—N5	1.3866 (12)	C3—H3C	0.9800
N5—C2	1.2873 (15)	C4—H4A	0.9800
N6—C1	1.3309 (14)	C4—H4B	0.9800
N6—H6A	0.891 (17)	C4—H4C	0.9800

C1—N1—N2	105.52 (9)	N5—C2—C3	128.40 (10)
N3—N2—N1	112.53 (9)	C4—C2—C3	117.11 (10)
N2—N3—N4	105.28 (9)	C2—C3—H3A	109.5
C1—N4—N3	108.59 (9)	C2—C3—H3B	109.5
C1—N4—N5	120.58 (9)	H3A—C3—H3B	109.5
N3—N4—N5	130.82 (9)	C2—C3—H3C	109.5
C2—N5—N4	120.83 (9)	H3A—C3—H3C	109.5
C1—N6—H6A	121.1 (10)	H3B—C3—H3C	109.5
C1—N6—H6B	114.8 (10)	C2—C4—H4A	109.5
H6A—N6—H6B	123.9 (14)	C2—C4—H4B	109.5
N6—C1—N1	127.15 (11)	H4A—C4—H4B	109.5
N6—C1—N4	124.77 (10)	C2—C4—H4C	109.5
N1—C1—N4	108.08 (9)	H4A—C4—H4C	109.5
N5—C2—C4	114.48 (10)	H4B—C4—H4C	109.5

C1—N1—N2—N3	−0.23 (12)	N2—N1—C1—N4	0.45 (11)
N1—N2—N3—N4	−0.08 (12)	N3—N4—C1—N6	179.91 (10)
N2—N3—N4—C1	0.37 (11)	N5—N4—C1—N6	−1.31 (16)
N2—N3—N4—N5	−178.25 (10)	N3—N4—C1—N1	−0.52 (12)
C1—N4—N5—C2	−176.51 (10)	N5—N4—C1—N1	178.26 (9)
N3—N4—N5—C2	1.97 (17)	N4—N5—C2—C4	179.59 (9)
N2—N1—C1—N6	−179.99 (11)	N4—N5—C2—C3	−1.35 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6A···N2ⁱ	0.890 (16)	2.200 (17)	3.0600 (16)	162.6 (13)
N6—H6B···N1ⁱⁱ	0.876 (15)	2.118 (15)	2.9770 (16)	166.4 (14)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₄H₈N₆
M_r	140.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	93
a, b, c (Å)	7.488 (2), 7.4238 (19), 11.997 (3)
β (°)	97.145 (3)
V (Å³)	661.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.43 × 0.43 × 0.33

Data collection
Diffractometer	Rigaku Saturn724+ diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5172, 1520, 1334
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.088, 1.00
No. of reflections	1520
No. of parameters	101
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.17

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6A···N2ⁱ	0.890 (16)	2.200 (17)	3.0600 (16)	162.6 (13)
N6—H6B···N1ⁱⁱ	0.876 (15)	2.118 (15)	2.9770 (16)	166.4 (14)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+2, −y, −z+1.

Acknowledgements

This work was supported financially by the State Key Laboratory of Explosion Science and Technology in Beijing Institute of Technology, China (No. ZDKT08–01).

References

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Galvez-Ruiz, J. C., Holl, G., Karaghiosoff, K., Klapotke, T. M., Lohnwitz, K., Mayer, P., Noth, H., Polborn, K., Rohbogner, C. J., Suter, M. & Weigand, J. J. (2005). Inorg. Chem. 44, 4237–4253. Web of Science CSD CrossRef PubMed CAS Google Scholar
Gaponnik, P. N. & Karavai, V. P. (1984). Khim. Geterotsikl. Soedin. 12, 1683–1686. Google Scholar
Joo, Y.-H., Twamley, B., Garg, S. & Shreeve, J. M. (2008). Angew. Chem. Int. Ed. 47, 6236–6239. Web of Science CSD CrossRef CAS Google Scholar
Lyakhov, A. S., Voitekhovich, S. V., Ivashkevich, L. S. & Gaponik, P. N. (2005). Acta Cryst. E61, o3645–o3647. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar